WO2004036656A2 - Procede d'analyse non destructif pour determiner la qualite d'une pile solaire, et son application - Google Patents

Procede d'analyse non destructif pour determiner la qualite d'une pile solaire, et son application Download PDF

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Publication number
WO2004036656A2
WO2004036656A2 PCT/DE2003/003372 DE0303372W WO2004036656A2 WO 2004036656 A2 WO2004036656 A2 WO 2004036656A2 DE 0303372 W DE0303372 W DE 0303372W WO 2004036656 A2 WO2004036656 A2 WO 2004036656A2
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WO
WIPO (PCT)
Prior art keywords
solar cell
quality
analysis method
parameters
semiconductor layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/DE2003/003372
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German (de)
English (en)
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WO2004036656A3 (fr
Inventor
Ilka Luck
Eveline Rudigier
Roland Scheer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hahn Meitner Institut Berlin GmbH
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Hahn Meitner Institut Berlin GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hahn Meitner Institut Berlin GmbH filed Critical Hahn Meitner Institut Berlin GmbH
Priority to AU2003301460A priority Critical patent/AU2003301460A1/en
Priority to DE50311501T priority patent/DE50311501D1/de
Priority to AT03808673T priority patent/ATE430991T1/de
Priority to EP03808673A priority patent/EP1556900B1/fr
Publication of WO2004036656A2 publication Critical patent/WO2004036656A2/fr
Publication of WO2004036656A3 publication Critical patent/WO2004036656A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering

Definitions

  • Non-destructive analysis method for determining the quality of a solar cell and application thereof.
  • the invention relates to a non-destructive analysis method for determining the quality of a solar cell using a data combination from an optical Raman spectroscopy to determine the structural properties of a semiconductor layer and to applications thereof.
  • IV characteristics current-voltage characteristics
  • the quotient of the maximum electrical power output to the radiated light output results in the open circuit voltage ("open terminal voltage"), the short-circuit current and current and voltage at the point of maximum power.
  • the so-called “fill factor” is calculated from the quotient of the maximum power to the load-free power, which is essentially determined by the recombination of the charge carriers as well as by parallel and series resistances.
  • the electronic properties of a semiconductor layer can be checked and ascertained using the measurement method of admittance spectroscopy. This provides information about electrically active defect states and the nature of the heterojunctions in the semiconductor layer produced by measuring the frequency and temperature-dependent complex AC conductance. The time development of the space charge zone capacity is measured by determining the imaginary value of the admittance. From publication II: "Defect Distribution of CulnS 2 Solar Cells from Different Preparation Processes as Determined by Admittance Spectroscopy" by K.Siemer et al.
  • FWHM half-value width
  • the defect phase can be determined by X-ray diffraction (XRD) as an in-situ measurement method.
  • XRD X-ray diffraction
  • the conversion coefficient as a measurement variable indicates the proportion of the laser light yield which is converted into the difference frequency per absorbed laser power density in the measurement object through the interaction with the measurement object.
  • this is also a structural parameter of the semiconductor material that allows access to existing electrical defects.
  • these complex processes which are always used jointly and exclusively for monocrystalline semiconductor material for analysis, usually do not work non-destructively and therefore cannot be integrated into line production. It is also not possible to draw a conclusion from the structural characterization of a semiconductor material that can be determined with this known method, regarding its characteristic electronic parameters and the electrical properties of a finished-processed solar cell built up on the semiconductor layer.
  • the object of the present invention to specify an analysis method of the type described at the outset which, based on the current knowledge of the structural parameters of a semiconductor layer, permits high-quality conclusions to be drawn about the electrical properties of a solar cell built up on the semiconductor layer.
  • the analysis method which is as simple as possible and inexpensive to implement, should work quickly and non-destructively and be applicable to both crystalline (mono- and polycrystalline) manifestations of semiconductor material as an absorber layer in the solar cell. Furthermore, integration into a production line should be possible by examining just completed semiconductor layers before the next work step. In an expansion of the requirements for the invention, it should also be possible be related to the electronic properties of the absorber layer in order to support the conclusions.
  • the solution to this problem is a non-destructive analysis method for determining the quality of a solar cell using a data combination from an optical Raman spectroscopy to determine the structural properties of a semiconductor layer and at least an electrical current-voltage measurement under the influence of lighting to determine the electrical properties of a solar cell , whereby directly after the generation of the semiconducting absorber layer of the solar cell, measurement data are recorded with Raman spectroscopy and converted into characteristic structural parameters, which are correlated and evaluated with characteristic electrical parameters of a solar cell that are predefined as a function of the semiconductor layer type, in order to predict the electrical properties of the finished processed solar cell.
  • the structural properties of a semiconductor layer are related to the electrical properties of a solar cell based on the semiconductor layer as the absorber layer. This makes it possible to draw conclusions about the later electrical properties of the finished solar cell directly after the production of the absorber layer by simply determining the structural layer properties by means of Raman spectroscopy.
  • a simple and quick to use and non-destructive quality control is possible directly after the production (ex-situ) of an absorber layer, which can be used to draw conclusions about the expected, decisive quality of the solar cell via the current structural parameters.
  • a Raman analysis only has to be carried out on the absorber layer currently being produced, so that only one measurement method from the combination in the analysis method has to be used in concrete terms.
  • the structural parameters derived from the measurement data currently received are then only included for a solar cell correlated graphically or numerically, for example, graphically or numerically, with the corresponding semiconductor layer type known characteristic parameters for the electrical properties (“electrical parameters”) in order to obtain an accurate prediction of the quality of the finished processed solar cell.
  • the characteristic parameters for the electrical properties can be obtained, for example, from measurements on corresponding
  • the measurement methods combined with Raman spectroscopy are used in the invention for the development of comparison values and, as it were, used as data-providing background methods, which results in a significant simplification for the practical application of the analysis method according to the invention.
  • the quality rating of a fully processed solar cell can be made even more meaningful if, according to a continuation of the invention in the non-destructive analysis method, an additional data combination from admittance spectroscopy under the influence of temperature to determine the electronic properties of a semiconductor layer and a correlation and evaluation of the current structural parameters with a given depending on the semiconductor layer type characteristic electronic parameters for verification of the forecast.
  • the statements about the electronic properties of the absorber layer produced in the solar cell are used to verify and reinforce the knowledge about their expected electrical properties. In the course of the method, this can look such that the currently determined characteristic structure parameters for the crystal quality are initially assigned to the characteristic electrical parameters for the electrical properties of the solar cell for the corresponding semiconductor layer type.
  • the non-destructive analysis method claimed can be determined by determining the full width at half maximum as a characteristic structural parameter for the crystal quality of the absorber layer, by specifying the open circuit voltage, the efficiency or the fill factor as a characteristic electrical parameter for the electrical quality of the solar cell and by specifying the Defect density can be carried out as a characteristic parameter for the electronic quality of the semiconductor layer.
  • the half-value width which results from the evaluation of the Raman data, is a meaningful characteristic parameter for the crystal quality produced.
  • the smaller the half width the better the crystallinity of the semiconductor layer.
  • the suitability or unsuitability of a semiconductor layer produced for further processing can be decided directly. It is advantageous according to a next development of the invention if there is an indication of a limit value for the characteristic structural parameters for the crystal quality of the absorber layer. The test result then only results from a simple comparison of numerical values.
  • the current measurement data is recorded, stored and correlated automatically.
  • This enables a time-optimized and error-free analysis of the semiconductor layer produced.
  • a Integration of the analysis method into a production line of a solar cell is provided. Quality control is thus carried out in situ in the manufacturing process of a solar cell by means of a Raman spectroscopy carried out ex situ after the production of the absorber layer before further processing of the absorber layer.
  • the influence of the analysis results on the further treatment of a currently produced absorber layer is particularly important from an economic point of view. In this way, high reject rates for the finished processed solar cells and after quality control on a process step that is recognized as poorly absorber layer can be avoided. Material and time can be saved. In particular, these advantages come into play if, after a further application, the non-destructive analysis method is used to determine the quality of a solar cell with an absorber layer made of a polycrystalline, hetero-bonded semiconductor material. This enables, for example, the ability to assess the quality of polycrystalline thin-film solar cells made of temporary or quaternary semiconductor materials at an early stage with regard to the quality of the active absorber layer, so that it can be removed from the production line immediately after preparation, if necessary.
  • the claimed analysis method can be used to determine the quality of a solar cell with differently produced absorber layers.
  • the absorber layers or samples to be examined can thus originate from different manufacturing processes.
  • the invention thus provides a universal analysis method for predictive quality control of solar cells, which is not limited to one type of manufacture for the absorber layer, but can be applied to various manufacturing methods. Diagrams shown in the individual figures are explained in more detail below for further understanding of the invention. It shows:
  • FIG. 1 Raman spectra at different open circuit voltages
  • FIG. 2 shows a correlation between the half-value width and the open circuit voltage
  • FIG. 3 shows a correlation between the half-value width and the fill factor
  • FIG. 4 shows a correlation between the half-value width and the defect density.
  • Raman spectra are shown in the diagram according to FIG.
  • the scattering intensity of the irradiated semiconductor layer (“Intensity” au) is plotted against the wave number ("Raman shift” in cm “1 ).
  • the evaluation method of these spectra is based on a mathematical function (solid line) that is used to fit the original data (line with points)
  • the Raman spectra were recorded for a semiconductor material of the copper indium disulfide type (CIS A Mode, CulnS 2 ).
  • the spectrum a is obtained if an open circuit voltage of 752 mV is determined on the sample by current-voltage measurement Analogously to this with other stoichiometries, there is an open circuit voltage of 715 mV for spectrum b and an open circuit voltage of 685 mV for spectrum c.
  • the dashed horizontal line in the Raman spectra represents the half width (FWHM) as characteristic parameters for the crystal quality of the semiconductor material.
  • a check of the correspondingly processed absorber layer using Raman spectroscopy then provides information about the effectiveness of the measures taken. If the limit is undershot, the absorber layer has the structural quality required for the desired electrical quality of the solar cell, without corrective measures, and can be processed immediately in the production line. A faulty absorber preparation can be excluded.
  • FIGS. 2 and 3 show the relationship between the characteristic parameter for the crystal quality (half width FWHM) obtained from Raman spectroscopy and the electrical properties of the solar cells examined.
  • FIG. 2 shows the relationship between the full width at half maximum FWHM and the open circuit voltage (Voc in mV) as a characteristic electrical parameter for the electrical properties of the solar cell. A tendency can be clearly seen (dashed curve). Up to a maximum FWHM of about 3.4 cm "1, a saturation region having a high open-circuit voltage Voc can be seen.
  • Absorber layers of said type CIS thus show up to a half-width of about 3.4 cm" 1 is a correlation with a satisfactorily high open-circuit voltage Voc of the corresponding solar cell and thus a sufficiently high crystalline quality for further processing. From this particular half-value width, however, the open circuit voltage Voc rapidly deteriorates with a widening half-value width. Absorber layers with half-widths in this range would therefore be due insufficient structural quality can be sorted out, since they would cause too low open circuit voltages in the finished processed solar cell.
  • FIG. 3 shows a diagram with a trend similar to the diagram according to FIG. 2, but here the fill factor (FF in%) is a further relevant electrical parameter for the electrical properties
  • Parameters for the electrical properties of the finished solar cell are derived. They can also be used to verify each other
  • Quality assessment based on the currently determined half-value width of the absorber layer can be used.
  • the diagram according to FIG. 4 shows the relationship between Raman spectroscopy and the electronic properties of a semiconductor layer, which can be used as an absorber layer. These were determined from admittance measurements.
  • a characteristic electronics parameter for the electronic properties of the defect density is here applied (in DOS 500 meV in cm “3 eV” 1) logarithmically over the half-width (FWHM in cm “1)
  • FWHM half-width
  • the procedure for quality prediction via the electronic proprietary Creation is carried out analogously to the procedure for assessing the electrical properties. Both quality selection methods, electrical and electronic, can be used for mutual confirmation.

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  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Photovoltaic Devices (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Testing Or Measuring Of Semiconductors Or The Like (AREA)

Abstract

Les procédés d'analyse de l'état de la technique ne permettent pas d'établir de corrélation entre les propriétés structurelles d'une couche de semi-conducteur et les propriétés électriques d'une pile solaire montée sur celle-ci. Le procédé d'analyse de l'invention se base sur une spectroscopie Raman rapide et non destructive qui permet de déterminer des paramètres structurels significatifs (FWHM) relatifs aux propriétés structurelles d'une couche d'absorption traitée, dans une pile solaire. La connaissance de ces paramètres structurels permet alors d'établir une corrélation avec des paramètres électriques (Voc) pertinents vis-à-vis des propriétés électriques attendues de la pile solaire finie. On constate une corrélation linéaire entre les paramètres avec une zone de saturation de propriétés électriques satisfaisantes et une valeur limite d'une zone de propriétés électriques insatisfaisantes de la pile solaire. Le procédé d'analyse de l'invention permet ainsi de déterminer la qualité électrique de la pile solaire finie, en connaissant uniquement les paramètres structurels de la couche d'absorption. En fonction de cela, on peut décider in-situ sur une chaîne de production de piles solaires par exemple polycristallines à hétérojonction, si une couche d'absorption analysée ex-situ doit subir un traitement ultérieur ou doit être retirée de la chaîne de production.
PCT/DE2003/003372 2002-10-13 2003-10-09 Procede d'analyse non destructif pour determiner la qualite d'une pile solaire, et son application Ceased WO2004036656A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU2003301460A AU2003301460A1 (en) 2002-10-13 2003-10-09 Non-destructive analysis method for determining the quality of a solar cell, and application of the same
DE50311501T DE50311501D1 (de) 2002-10-13 2003-10-09 Zerstörungsfreies analyseverfahren zur güteermittlung einer solarzelle und anwendung davon.
AT03808673T ATE430991T1 (de) 2002-10-13 2003-10-09 Zerstörungsfreies analyseverfahren zur güteermittlung einer solarzelle und anwendung davon.
EP03808673A EP1556900B1 (fr) 2002-10-13 2003-10-09 Procede d'analyse non destructif pour determiner la qualite d'une pile solaire, et son application

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10248504.6 2002-10-13
DE10248504A DE10248504B4 (de) 2002-10-13 2002-10-13 Zerstörungsfreies Analyseverfahren zur Güteermittlung einer Solarzelle auf Chalkopyritbasis

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WO2004036656A2 true WO2004036656A2 (fr) 2004-04-29
WO2004036656A3 WO2004036656A3 (fr) 2004-06-24

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EP (1) EP1556900B1 (fr)
AT (1) ATE430991T1 (fr)
AU (1) AU2003301460A1 (fr)
DE (2) DE10248504B4 (fr)
ES (1) ES2325155T3 (fr)
WO (1) WO2004036656A2 (fr)

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US8633378B2 (en) 2006-09-04 2014-01-21 Mitsubishi Heavy Industries, Ltd. Method of setting conditions for film deposition, photovoltaic device, and production process, production apparatus and test method for same
CN111769050A (zh) * 2020-07-03 2020-10-13 南通大学 一种利用拉曼光谱检测钙钛矿太阳能电池效率的方法

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DE102009024377B4 (de) 2009-06-09 2011-02-10 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Zerstörungsfreies Analyseverfahren zur Güteermittlung einer Dünnschichtsolarzelle mittels Photolumineszenzspektroskopie
JP7420204B2 (ja) * 2022-02-25 2024-01-23 株式会社プロテリアル 窒化珪素基板の評価方法、評価装置、及び評価システム

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8633378B2 (en) 2006-09-04 2014-01-21 Mitsubishi Heavy Industries, Ltd. Method of setting conditions for film deposition, photovoltaic device, and production process, production apparatus and test method for same
CN111769050A (zh) * 2020-07-03 2020-10-13 南通大学 一种利用拉曼光谱检测钙钛矿太阳能电池效率的方法

Also Published As

Publication number Publication date
ES2325155T3 (es) 2009-08-27
EP1556900A2 (fr) 2005-07-27
WO2004036656A3 (fr) 2004-06-24
EP1556900B1 (fr) 2009-05-06
DE10248504B4 (de) 2008-01-10
ATE430991T1 (de) 2009-05-15
AU2003301460A8 (en) 2004-05-04
DE50311501D1 (de) 2009-06-18
AU2003301460A1 (en) 2004-05-04
DE10248504A1 (de) 2004-04-22

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